Catalyst conversion system



f 2 sheets-sheet 1 D. E. PAYNE CATALYST CONVERSION SYSTEM Filed Dec. 2 0, 1938 Aug. 25, 1942.

INVENTOR Aug. 25, 1942. D. PAYNE I CATALYST CONVERSION SYSTEM Filed Dec. 20, 1958 2 Sheets-Shea?l 2 77207@ nzflala,

INVENTOR Patented Aug. 2 5, 1942 CATALYST CONVERSION SYSTEM l Donald E. Payne, Chicago, lll., assignor to Standard Oil Company, Chicago, Ill., a corporation of Indiana Application December zo, 193s, serial No. 246,862

' c claims. (c1. 19e- 52) This invention relates to a catalytic system and it pertains more particularly to systems of catalytic cracking, dehydrogenation, polymerization, etc., wherein carbon is deposited on the catalyst and has to be burned from the catalyst in a regeneration step.

In catalytic cracking systems the problem o catalyst regeneration is most diiiicult because rapid oxidation of the deposited carbon tends to overheat the catalyst and render it inactive. The so-called Houdry Process has sought to solve this problem by the provision of an extremely complicated, cumbersome and expensive arrangement of finned tubes closely spaced throughout a .catalyst chamber which is iilled with contact material. Even inthe Houdry system, however, the catalyst particles may be an inch or more from a heat absorbing surface, and great care must be exercised in proportioning the amount of flue gas used to dilute the regenerationair to prevent overheating in the regeneration step. An object of my invention is to provide a ysimple means for effecting catalytic conversion vwhich will provide sumcientcontact for the catalytic conversion step, and which will at the same time avoid the` least as short a cycle as the catalyst conversion step so that one catalyst unit will'be ready to go on stream as soon as an adjacent catalyst system requires regeneration.

A further objectv is to provide an improved by the on stream conversion may be effectedv by series flow and the purging and regeneration may be eiected by parallel ilow. Other objects will be apparent as the detailed description of my invention proceeds. l

In practicing the'invention I form my catalyst into tubular liners which are inserted into the catalyst tubes to form a substantially continuous liner therefor. The thickness of these liners I is preferably about one-eighth to one-quarter inch so that they may readily absorb heat from' the tubes for the purpose ci catalytic conversion. and so that during the regeneration step the heat of carbon oxidation may be quickly dissipated to said tubes without fusingr the catalyst or causing anyv loss of catalyst activity. The tubes may be exposed lto hot gases in or from the convection sectionoiv a furnace or may be immersed in a iluid such as mercury, diphenyl, molten lead, a fused salt bath, etc. y

The heated charging stock is passed through one set of lined tubes in series to effect turbulent ilow and to insure suicient contact, while an `adjacent set of tubes is undergoing purging and regeneration with the tubes connected in parallel. When the activity of the catalyst in the rst covered from said steam and returned to the system. Other features and advantages oi* my imheat transfer system for insuring substantially l constant temperatures during the catalytic conlversion step and for preventing overheating of the catalyst during the regeneration step.

A further object is to provide an improved purging system which will eiect the recovery of all hydrocarbons remaining in the Asystem at the clos'e of any cycle, and which will eliminate any oxygen-containing gases from the system' j.prior to the introduction of hydrocarbons for conversion..

A further object is to provide an improved means for charging catalysts into catalyst tubes,

proved system will be apparent from the tollowing detailed description, and from, the annexed drawings which form a part of this speciiicatlon, and in which- Fig. 1 is a flow diagram of my improved catalytic conversion system;

2 is an isometric view of a tubularcatalyst liner;

Fig. v3 is a longitudinal cross section of a catalyst tube illustrating themethod ot positioning the liners therein; Y

Fig. 4 is a transverse crossV section of 'the catalyst tube and liner;

Fig. 5 is a transverse cross section of the catalyst tube and* a modied'liner designed to give additional contact area and turbulent w; and

Fig. 6 is a detail partly in section showing the return bend unit and the method of attaching tively. v

tubes from series toparallel and vice versa, where- The invention will be described as applied to the are purged with` steam (or ue gas) and hydrocarbons are re'` catalytic cracking of Mid-Continent gas oil, although it should be understood that any other lcharging stock may be used. The invention is larly when such processes lead to theformation l5 of carbon in the catalyst and require regeneration by burning such carbon with an oxygencontaining gas. The invention may be applicable to other processes than those of hydrocarbon conversion, as will be apparent from the following detailed description.

The charging stock is introduced by pump I through line I I into the coils I2 of pipe still I3, where it is heated to a temperature of about 850 to 1000 F., preferably about 925 F. At this 2 temperature and at a pressure of from about atmospheric to 50 pounds per square inch the Vaporized charging stock is conducted through transfer line I4, valve I and line I6 to catalyst tubes I1.

The catalyst tubes are preferably made of steel or chromium alloy and may be about 20 or 30 feet long and about 1 to 3 inches inside diameter. Each tube is provided with continuous catalyst liners IB in the form of tubular sleeves the outside diameter of which is only slightly less than the inside diameter of the tube. I These sleeves are about t@ to %A inch, preferably about 1/4 mch, in thickness and they may be made in suitable lengths of from about 3 to 12 inches. These tubular sleeves may have a smooth cylindrical inner surface or they may be internally corrugated or otherwise deformed to provide additional surface contact areaV and to promote turbulent :Iow of gases.

In Fig. 2 I have shown a simple cylindrical sleeve; a plurality of which are inserted in the catalyst tube as shown by Fig. 3 to form a continuous internal liner. Fig. 4 shows a cross sectionof such tube, and Fig. 5 shows a similar 50 cross section of a tube wherein the inner surface of the liner is provided with spiral corrugations I9. It should be understood that any other shape or form of catalyst liners may be used without departing from 'the spirit of the invention.

For catalytic cracking the tubular catalyst liners are preferably made from acid-treated clay of the type commonly marketed as Super Filtrol, such clays being commonly used for the decolorization of lubricating oils.' The acid treated clays may be used as such or they may be impregnated with oxides of various metals such as copper. cadmium, nickel, manganese, etc. Such clay is made into Aa thick slurry or paste and formed into tubes by any conventional means such, for instance, as a machine used for making tIlepIDe. These tubes are cut into the desired lengths, preferably about 6 inches, and are heated to a temperature suflicient to drive out moisture a'nd to give them the necessary rigidity and strength for handling. If the clay material itself does not offer sufficient strength an argillaceous or organic binder may be employed but I prefer to avoid the use of any materialswhich may decrease the porosity of the tube.

Instead of making these tubes from acid treated clay I may employ silica gel impregnated with metal oxides of various metals such as aluminum,

`copper, nickel, cadmium, manganese, etc. Here 5 again I may employ any suitable binder which maybe necessary to prevent the finished tube yfrom being too fragile. Naturallyoccurring clay such as fullers earth, Death Valley clay, montmorillonite, bentonite, Wilkinite, etc., particu- 10 larly when acid treated, and natural zeolites with alkali metals replaced by copper, cadmium, aluminum, manganese, etc., boron silicates, activated aluminum silicates, etc. are further examples of such catalytic cracking catalysts.

For dehydrogenation the catalyst sleeves may be made of chromium oxides or mixtures of chromium oxides with other metal oxides such as copper oxides. Alternatively; they may be made of magnesium chromite, cobalt-nickel borate or any other dehydrogenation catalyst. Here, as

in the case of the cracking catalysts, suitable binders may be employed if the catalytic material itself does not result in a finished tube which can be conveniently handled. For polymerization the tubes may be made with silica,.kieselguhr, etc. or' other suitable carrier subsequently impregnated with phosphoric acid. Other examples of catalysts and catalyst carriers wil be evident from the above examples.

The tubes containing thev catalyst sleeves may be mounted in the convection chambers of furnace I3 in a chamber through which hot furnace gases are passed. Alternatively, they may be enclosed in a constant temperature chamber 20 which in the present case is a vessel designed to hold a fused mixture of NaNOa (sodium nitrate), -KNOa (potassium nitrate) and NaNO: (sodium nitrite), or to hold mercury at afpressure' oi' about 100 to 1-50 pounds per square inch. The

40 tubes may be welded into such chambers as indicated in Fig. 6, the ends of the tubes projecting therefrom and being provided with flanges to which return bends 2I may be bolted. The return bends preferably form a connection between these tubes and a header which will be hereinafter described, each return bend assembly being provided with ayalve 22 and pipe extension 23 whichl makes a right angle bend so. that its flanges may be bolted to pipe 24 in a plane perpendicular to the flanges on tubes I1. This arrangement makes possible the removal of each return bend assembly for the withdrawal or introduction of catalyst sleeves.

The fused salt bath, mercury, diphenyl or other 5 heat exchange fluid in chamber 20 maintains the temperature of all of the catalyst tubes at a constant value of about 925 F. The number and length of tubes will necessarily 'vary with the particular reaction and charging stock, but in order to insure suicient contact of hot hydrovapors are taken through line 32 and condenser 33 to stabilizer 34 which is likewise provided with suitable reflux means 35 and reboiler means 3l.

Gasoline is withdrawn from the base of the stabilizer through line 31.

The gases withdrawn from the top of the sta--y bilizer through line 38 are partially condensed in cooler 39 and introduced into separator or deethanizer 40, the hydrogen, methane and -most 0i the C2 hydrocarbons being withdrawn throughA line 21 through lines 25, 25a, 25h, etc. Similarly,

version. The.Cs-C4 fraction may be converted by alkylation with concentrated sulfuric acidf or other catalysts or may be employed in a thermal or catalytic gas reversion or polymerization system.

As the catalytic cracking of gas oil proceeds carbon is deposited upon the catalyst, and after a length of run, which may vary from about minutes to 8 hours, preferabiyone-half hour, tL one hour, it is necessary to-regenerate the catalyst material. The length of run will, of course depend upon the number and size of catalyst tubes as well as on the particular catalyst and the nature of the stock charged. The sequence of steps for regeneration may be as follows:

Valves I5 and 26 are closed while valvesISa and 26a are being simultaneously opened, so that thehot gas oil vapors are cracked in chamber 28a, while the tubes in chamber 20 are being purged and regenerated. Valves 22 which have heretofore been closed are immediately and simultaneously opened and the catalyst tubes are purged with steam which is introduced through line 42,v branch line 44, valve 45, line 46 and manifold 41. This steam passes` through the return bend assemblies from one end of the tubes to return bend assemblies on the opposite. ends of the tubes, and from them is withdrawn through manifold 48, line 49, valve 50 and line 5I to cooler 52 and'water separator 53. Condensed steam. is-withdrawn through line 54 and lrecovered gas oil is returnedby pump 55 (controlled by suitable liquid level control means) through line 56 Ato charge line II. Flue gas may, of course, be u'sed instead of steam for purging. and the g'as oil may be separated therefrom by conventional means.

VThe steam plu'ging step only requires a few seconds after which valves 45 and 50 are closed and oxygen-containing gas is introduced by pump 51, line 58, valve 59, line 46 and manifold 41 through the catalyst tubes, .the spent regeneration gases being withdrawn through manifold 48, line 49, valve 60, line 6I and line 62. 1f the fused salt bath, mercury or other heat exchange uid surrounds the catalyst tubes I1, this regeneration may be eilected with air since the close proximity of the catalyst to the tube walls provides for the rapid removal of the 'heat of regeneration, and thus prevents overheating. troduce flue gas with the air to prevent too rapid an oxidation. Immediately after regeneration valve 59 is closed and valve 45 is opened so that the oxygen-containing gases are swept out of the system by steam. Valves 22 are then closed and I may, of course, in-

tubes -I1 are again placed on stream by opening i valves I5 and 26. l

When the gas oil stream is directed back to the tubes in chamber 26, the tubes in chamber 26a may be regenerated, as hereinabove described. Itshould be understood that any number o units rnay be connected to line I4 by lines I6, Ita, |617, etc., and that each of these units discharges into :the regeneration and purging lines are maniiolded for use on any number of catalyst tube assemblies. 'I'hus one assembly may be on stream while two assemblies are regenerated, or vice versa. and any desired balance of on-stream-to-regeneration cycles may be used.

It should be particularly noted that the cracking is eiected with the tubes connected in series, while regeneration is eiected with the tubes connected in parallel. When large numbers of tubes areV thus employed it will be seen that the Atime v'required for purging is only a very small fraction terial is in close proximity to the pipes so that the heat of lregeneration is eiectively transferred thereto; this prevents overheating of the catalyst and makes possible a rapid regeneration. The heat liberated during the regeneration step may be stored in the pipes and in the heat exchange iiuid in chamber 20 to supply theheat of cracking when the assembly returns on stream. Any

excess heat over and above that required for cracking may be carried away by hot regeneration gases, or, if desired, the mercury or other liquid in chamber 20 may be boiled under pressure of about pounds per square inch and condensed in a steam power unit so that the excess heat may be vused-to furnish power for driving the pumps and compressors.

While I prefer to operate in 'series on stream and in parallel for regeneration, it should' be understood that the parallel flow may likewise be used for the cracking step by simply closing valves I5 and 26, introducing the hot gas oil vapors through line 63 and valve 64 in manifold 41 and withdrawing the reaction products through manifold 48, line 49, line 65 and valve 66 to line 21.

vThe valves throughout my system may be operated by conventional electrical, pneumatic or hydraulic means from a central control room.

In the above description I have described the operation of my invention as applied to the catalytic cracking of gas oilA with a clay catalyst. Other catalysts'may have other optimum temperatures, but they will usually be `about 850 to 925 F.

When the invention is applied to catalytic dehydrogenation the temperatures and pressures are approximately the same as those hereinabove described for catalytic cracking, and as in the ease of cracking, low pressures are particularly ad- `vantageous. For polymerization with phosphoric v acid deposited on kieselguhr the temperature should be about 250 to 600 F. and the pressure about atmospheric to 50 pounds per square inch.

The use of catalyst liners in steel ,tubes is also particularly advantageous for high pressure reactions, my apparatus being particularly advantageous since it avoids the necessity of large reaction chambers under such high pressure conditions.

While r have described in detail certain pre-J ferred embodiments of myinvention it should be understood .that I do not limit myself to any of the details hereinabove set forth except as dened by the following claims which should be construed as broadly as the prior art will permit.

I claimt 1. The method o f catalytically converting hydrocarbons' in processes wherein carbon is deposited on the catalyst which comprises heating said hydrocarbons to reaction temperature, and passing the heated hydrocarbons through catalyst-lined tubes connected in series whereby carbon is deposited upon the catalyst, purging said system, regenerating said catalyst by burning said carbon therefrom with said tubes connected in parallel, and effecting regeneration and purging in a period of time substantially equal to the time of catalytic conversion.

2. The method of catalytically converting hydrocarbons in processes wherein carbon is `de posited upon the catalyst, which method comprises, heating said hydrocarbons to reaction temperature and passing them through tubesv lined with catalyst material and connected in series, purging said tubes with. an inert gas while they are connected in parallel, separating hydrocarbons from the inert gas, recycling said hydrocarbons to the heating step, regenerating the catalyst in said tubes while they are connected in parallel, purging the regeneration gases from said catalyst tubes while vthey are connected in parallel and catalytically converting further amounts of hydrocarbons with said tubes connected in series. y

3. In a system for the catalytic conversion of hydrocarbons, a plurality of catalyst lined tubes arranged substantially parallel to each other, a plurality of return bend units each provided with a return bend and a draw-off line, a manifold at each end of said tubes, means for connecting the return bends of each unit to adjacent tubes for effecting a series connection ofthe tubes, means for connecting the draw-off line of each return bend unit to the manifold adjacent that end of the tubes, a valve between each retum bend and its respective manifold whereby the tubes may be effectively connected for both parallel and series flow, conduits for introducing vapors into and withdrawing vapors from said tubes while they are connected in series, means for closing said last-named conduits, means for introducing gases into said tubes from one of said manifolds, and meansor withdrawing gases from said tubes through the other of said manifolds.

4. The apparatus of claim 3 which includes flanged connections between return bends and tubes which are at right angles to iiange connections between said draw-o lines and manifolds respectively.

5. A catalytic conversion system which comprises means for heating a hydrocarbon oil to a temperature of about 850 to 1000 F., a plurality of catalyst tube systems, a plurality of tubes in each tube system, liners in said tubes comprising catalytic metal oxides, means for selectively connecting the tubes in each system for series or parallel iiow, means for passing heated charging stock through said tubes in series iiow in one system while-another system is being regenerated .in parallel flow, means for regenerating the 'rst system in parallel flow and simultaneously psing the heated oil to the second system in series ow, and means for recovering gas oil, gasoline and gases from the reaction products.

6. The system defined by claim 5 wherein the liners in the catalyst tubes comprise pre-formed catalyst sleeves consisting essentially of silica and alumina.

' DONALD E. PAYNE. 

